JP2000072969A - Thermosetting resin composition, prepreg, laminated board, and printed circuit board - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a compsn. for producing a laminated board which exhibits no degradation in insulating properties and no decrease in reliability by forming a thermosetting resin compsn. contg. a metal complex dye. SOLUTION: This compsn. is prepd. by compounding a thermosetting resin with a metal complex dye of formula I (wherein A+ is a cation represented by formula II) in an amt. of 2 wt.% or lower (based on the compsn.). A varnish is prepd. from the compsn. by using or without using a solvent. A fibrous substrate is impregnated with the varnish and dried to give a prepreg. Several pieces of prepreg are laminated by using the above-formed prepreg as the outermost layers and then pressed under heating to give a laminated board. An epoxy resin, a phenol resin, a polyimide resin, etc., can be used as the thermosetting resin, an epoxy resin being prepf. The epoxy resin is a phenol novolak epoxy resin, a resol epoxy resin, a bisphenol epoxy resin, or the like. A curative (e.g. dicyandiamide) and a cure accelerator (e.g. an imdazole compd.) are also used.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a thermosetting resin composition, a prepreg, a laminate, and a printed wiring board.

[0002]

2. Description of the Related Art A printed wiring board is formed by laminating one or a required number of prepregs obtained by impregnating and drying a varnish of a thermosetting resin composition on a fiber base material, and forming a laminate by heating and pressing. Then, a circuit is formed on the surface of the laminated board as a substrate to manufacture the laminated board. Usually, when manufacturing a laminate, metal foils such as copper foil are simultaneously laminated to form a metal-clad laminate, and the metal foil is etched to form a circuit. Therefore, in this specification, a laminate is meant to include a metal-clad laminate.

[0003] In recent years, printed wiring boards used for applications such as semiconductor mounting packages are mainly based on black. This is because the quality of wire bonding mainly using a gold wire can be easily identified, a high-quality appearance can be obtained, and ultraviolet rays are not transmitted to the opposite surface in the exposure process. When ultraviolet rays are transmitted to the opposite surface in the exposure step, the resist on the opposite surface is exposed to light, so that a so-called back blur occurs, which is not preferable. As a method of making the substrate black, a method of using a black fiber base material for a prepreg for manufacturing a laminate,
A method of blending a carbon-based pigment such as carbon black and spirit black into a thermosetting resin composition is known.

[0004]

However, in the method in which the substrate is made black using a black fiber base material, a sufficient ultraviolet shielding property cannot always be obtained because of the gaps in the fiber base material.
In addition, the fiber base material may not have sufficient blackness, and there is a problem in appearance. In addition, the method of blending a carbon-based pigment such as carbon black or spirit black into the thermosetting resin composition tends to cause a decrease in the insulation of the substrate and a decrease in the insulation between circuits due to electrolytic corrosion. (Hereinafter simply referred to as “reliability”).

[0005] The first aspect of the present invention is suitable for producing a laminated board which is black in appearance, can sufficiently shield ultraviolet rays, and has no decrease in insulation and reliability as a printed wiring board. An object is to provide a thermosetting resin composition. The invention according to claim 2 provides a prepreg suitable for producing a laminated board which is black in appearance, can sufficiently shield ultraviolet rays, and has no reduction in insulation and reliability as a printed wiring board. The purpose is to do. It is an object of the present invention to provide a laminate having a black appearance, capable of sufficiently shielding ultraviolet rays, and having no deterioration in insulation and reliability as a printed wiring board. An object of the invention described in claim 4 is to provide a printed wiring board having a black appearance and having no reduction in insulation and reliability.

[0006]

The present inventors have studied various thermosetting resin compositions by blending various black dyes in place of carbon-based pigments. As a result, the structural formula is shown by the following chemical formula (1). It has been found that, when the metal complex dye is mixed, the appearance of the laminate can be made black and the deterioration of insulation and reliability can be eliminated.

Embedded image

That is, the invention according to claim 1 is a thermosetting resin composition containing a metal complex dye represented by formula (1).

A second aspect of the present invention is a prepreg obtained by impregnating and drying a varnish of the thermosetting resin composition according to the first aspect on a fiber base material.

Further, the invention according to a third aspect is a laminate obtained by heating and pressing a prepreg construct including at least one prepreg according to the second aspect.

A fourth aspect of the present invention is a printed wiring board having a circuit formed on the surface of the laminate according to the third aspect.

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION The metal complex dye represented by formula (1) is a dye known as Solvent Black 27, and a commercially available metal complex salt dye can be used. As a commercially available product, Neo Super Black C-832 (Neo Su
per Black C-832) (chemical name: chromic acid (1-), [1-[(2-hydroxy-4
-Nitrophenyl) azo] -2-naphthalenolate (2
-)] 3- of [1-[(2-hydroxy-5-nitrophenyl) azo] -2-naphthalenolato (2-)]
[(2-Ethylhexyl) oxy] -1-propanamine hydrogen (1: 1) compound (Chromato (1-), [1-[(2-hydrox
y-4-nitrophenyl) azo] -2-naphthanolenolato (2-)] [1-
[(2-hydroxy-5-nitrophenyl) azo] -2-naphthanolenolato
(2-)]-, hydrogen.compd. With 3-[(2-ethylhexyl) oxy]-
1-propanamine (1: 1))) and those commercially available.

The thermosetting resin used as the base of the thermosetting resin composition may be a thermosetting resin widely used in the production of a laminate, and is not particularly limited. For example, an epoxy resin, a phenol resin, a bismaleimide resin, a polyimide resin, an unsaturated polyester resin, and the like can be given. Among them, an epoxy resin is preferably used. The epoxy resin may be any compound having two or more epoxy groups in the molecule. Examples thereof include phenol novolak epoxy resins, cresol novolac epoxy resins, resole epoxy resins, and bisphenol epoxy resins. Glycidyl ethers such as epoxy resin (phenolic epoxy resin), alicyclic epoxy resin, epoxidized polybutadiene, glycidyl ester type epoxy resin, glycidylamine type epoxy resin, isocyanurate type epoxy resin, flexible epoxy resin, etc. No. These polyfunctional epoxy resins may be used alone or in combination of two or more. When an epoxy resin is used as the thermosetting resin, a curing agent and a curing accelerator are blended to cure the epoxy resin. Examples of the curing agent include novolak-type phenol resins, dicyandiamide, acid anhydrides, and amines, and examples of the curing accelerator include imidazoles. These may be used alone or 2
More than one kind may be used in combination. Further, the curing agent and the curing accelerator are blended in a necessary range according to the amount of the polyfunctional epoxy resin used. When a thermosetting resin other than an epoxy resin is used, a curing agent required for each thermosetting resin is similarly compounded as necessary. In addition to a thermosetting resin and a curing agent to be blended if necessary, an inorganic filler can be blended from the viewpoint of improving mechanical properties and reducing costs by increasing the amount. As such an inorganic filler,
Alumina, finely divided silica, aluminum hydroxide, zirconium silicate, talc and the like can be mentioned.

The amount of the metal complex dye represented by the formula (1) is preferably 2% by weight or less in the thermosetting resin composition. Even if it is added in a large amount exceeding 2% by weight, the effect does not change. The lower limit of the amount is
It is appropriately selected so that the degree of black color of the laminated board is 25 or less in 1976 CIE lightness L ^* . 1976
If the CIE lightness L ^* exceeds 25, the degree of blackness tends to be insufficient and the ultraviolet shielding property tends to decrease.

The thermosetting resin composition according to the present invention is impregnated and dried on a fiber base material as a varnish to obtain a prepreg.
As the solvent used when forming the varnish, a conventionally known solvent that can dissolve the thermosetting resin to be used can be used, and there is no particular limitation. When a liquid thermosetting resin is used, it may be solventless. Examples of the solvent include water, methanol, ethanol, propyl alcohol, butyl alcohol, acetone, methyl ethyl ketone, toluene, xylene, dioxane, N, N dimethylformamide, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, and the like. May be used alone or in combination as needed.

The fiber base material used in the present invention may be a fiber base material generally used in the production of a laminate, and is not particularly limited. Among them, a glass woven fabric or a glass nonwoven fabric is preferably used from the viewpoint of characteristics such as heat resistance.

The method and manufacturing conditions for impregnating and drying the thermosetting resin composition varnish on the fiber base material to obtain a prepreg can be the same as those conventionally known for the base thermosetting resin. There is no particular limitation. The same applies to the method and conditions for manufacturing a laminate, and the method and conditions for manufacturing a printed wiring board by performing circuit processing on a metal-clad laminate.

When a plurality of prepregs are used in a material composition for manufacturing a laminate, at least one prepreg according to the present invention is used from the viewpoint of ultraviolet absorption.
You only have to use one. Also, in the configuration of the prepreg,
The position where the prepreg of the present invention is arranged is not particularly limited. However, from the viewpoint of easy identification of wire bonding quality and appearance, it is preferable that the prepreg according to the present invention be configured as the outermost layer.

[0018]

【Example】

Example 1 A brominated epoxy resin having an epoxy equivalent of 480 (using YDB-400 (trade name) manufactured by Toto Kasei Co., Ltd.) 100
Parts (parts by weight, the same applies hereinafter), dicyandiamide 3 parts, 2-
0.17 parts of ethyl-4-methylimidazole and 0.5 of a metal complex salt dye represented by the formula (1) (Chemical Synthetic Chemical Co., Ltd., Neo Super Black C-832 (trade name)) Parts of ethylene glycol monomethyl ether 25 parts and N, N dimethylformamide 25
The epoxy resin composition varnish was prepared by dissolving in a solvent consisting of parts. The prepared epoxy resin composition varnish was coated with a glass woven fabric having a thickness of 0.1 mm and a basis weight of 104 g / m ² (GA-7010S (trade name, manufactured by Nitto Boseki Co., Ltd.))
Was used to obtain a prepreg by impregnating so that the adhesion amount after the impregnation and drying was 50% by weight. Two prepared prepregs were stacked, and a copper foil having a thickness of 18 μm was placed on both surfaces thereof, and heated and pressed under reduced pressure at a temperature of 175 ° C. and a pressure of 3 MPa for 60 minutes to prepare a double-sided copper-clad laminate. A circuit was formed by etching the produced double-sided copper-clad laminate to produce a double-sided printed wiring board. The double-sided printed wiring board produced is based on black appearance of the board,
It was easy to determine the quality of wire bonding.

Comparative Example 1 An epoxy resin composition varnish was prepared in the same manner as in Example 1 except that 1.0 part of spirit black was used in place of the metal complex salt dye represented by the chemical formula (1). Prepared,
A prepreg was prepared, a double-sided copper-clad laminate was prepared, and a double-sided printed wiring board was prepared. In the produced double-sided printed wiring board, the appearance of the substrate was based on black, and it was easy to determine the quality of wire bonding.

Comparative Example 2 An epoxy resin composition varnish was prepared in the same manner as in Example 1, except that the metal complex salt dye represented by the chemical formula (1) was not added. Same as Example 1 except that this varnish was impregnated and dried in a black glass woven cloth (manufactured by Nitto Boseki Co., Ltd., GA-7010XB07 (trade name)) having a thickness of 0.1 mm and a basis weight of 104 g / m ^2. Then, an epoxy resin composition varnish was prepared, a prepreg was prepared, a double-sided copper-clad laminate was prepared, and a double-sided printed wiring board was prepared. In the produced double-sided printed wiring board, the appearance of the substrate was based on black, and it was easy to determine the quality of wire bonding.

The copper foil of the double-sided copper-clad laminate obtained as described above was entirely removed by etching, and this was irradiated with ultraviolet rays to examine the ultraviolet transmittance. A test pattern 2 circuit was formed on the double-sided copper-clad laminate by electrically connecting the front and back circuits with 100 holes of copper plated through holes having a distance between holes of 300 μm and a hole diameter of 0.5 mm, and a temperature of 85 ° C. and a relative humidity of 85 were formed. % Between the two circuits in a constant temperature and humidity chamber of 10%.
It was applied for 00 hours. Thereafter, the electrical resistance to corrosion was examined by measuring the insulation resistance between the two circuits. Table 1 shows these results.
Shown in

[0022]

[Table 1]

According to Table 1, in Example 1 in which the metal complex dye represented by the chemical formula (1) is mixed, the ultraviolet transmittance of the laminate is small, and the insulation is reduced by the electrolytic corrosion of the printed wiring board. No reliability indicates good reliability. On the other hand, in Comparative Example 1 in which a carbon-based pigment was blended in place of the metal complex dye represented by the chemical formula (1), although the ultraviolet transmittance was small, the insulation loss due to electrolytic corrosion was large. It shows that the reliability is not good. In Comparative Example 2 using a black glass woven fabric, it is shown that although the electrolytic corrosion resistance is good, the ultraviolet transmittance is large.

[0024]

According to the present invention, a prepreg according to the second aspect of the present invention is produced using the thermosetting resin composition according to the first aspect of the present invention, and the ultraviolet rays are sufficiently shielded by using the prepreg. And a laminated board based on black can be manufactured. And since this laminated board has good ultraviolet shielding property, it can be used as a printed wiring board by simultaneous exposure on both sides, and since there is no insulation deterioration due to electrolytic corrosion, it is excellent in reliability, and the quality of wire bonding is good. Identification is also easy.

Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat II (Reference) H05K 1/03 610 H05K 1/03 610S (72) Inventor You Murai You 1500 Ogawa, Oji, Shimodate-shi, Ibaraki Prefecture Hitachi Chemical Co., Ltd. F-term in the Shimodate factory (reference) 4F072 AA07 AB09 AB28 AD23 AE09 AF18 AG03 AG17 AH02 AH21 AJ04 AK05 AL13 4F100 AB01B AB17B AB40H AG00A AH02H AH03H AH08A AH08H AK01A AK53A AL06A04 J12 BA10 BA12 BA10A12 BA12 BA10A12 BA10 CC032 CD011 CD021 CD051 CD061 CD131 CD141 EL137 EN007 ES006 ET007 EU117 FD010 FD096 FD142 FD147 GF00 GQ00 HA05

Claims (4)

[Claims] 1. A thermosetting resin composition comprising a metal complex dye represented by the following chemical formula (1). Embedded image 2. A prepreg obtained by impregnating and drying a varnish of the thermosetting resin composition according to claim 1 on a fiber base material. 3. A laminate obtained by heating and pressing a prepreg construct containing at least one prepreg according to claim 2. 4. A printed wiring board comprising a circuit formed on the surface of the laminate according to claim 3.